US7764379B1 - Semiconductor laser natural gas analysis system and method - Google Patents
Semiconductor laser natural gas analysis system and method Download PDFInfo
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- US7764379B1 US7764379B1 US11/613,291 US61329106A US7764379B1 US 7764379 B1 US7764379 B1 US 7764379B1 US 61329106 A US61329106 A US 61329106A US 7764379 B1 US7764379 B1 US 7764379B1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 16
- 239000003345 natural gas Substances 0.000 title description 7
- 238000004868 gas analysis Methods 0.000 title 1
- 230000003595 spectral effect Effects 0.000 claims abstract description 25
- 238000012544 monitoring process Methods 0.000 claims abstract description 10
- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 238000001307 laser spectroscopy Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 80
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 13
- 239000013307 optical fiber Substances 0.000 claims description 13
- 230000010287 polarization Effects 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000004611 spectroscopical analysis Methods 0.000 description 15
- 239000000523 sample Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000013178 mathematical model Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/10—Arrangements of light sources specially adapted for spectrometry or colorimetry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
- G01J3/433—Modulation spectrometry; Derivative spectrometry
- G01J3/4338—Frequency modulated spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/12—Generating the spectrum; Monochromators
- G01J3/26—Generating the spectrum; Monochromators using multiple reflection, e.g. Fabry-Perot interferometer, variable interference filters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
- G01N2021/396—Type of laser source
- G01N2021/399—Diode laser
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/05—Flow-through cuvettes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
Definitions
- BTU Blunt Thermal Unit
- energy-content monitors are used to analyze the BTU content of natural gas at producing wells and transfer points, and also at the points of consumption.
- NIR near infrared
- GC gas chromatographs
- the hydrocarbons present in the natural gas are separated based on the retention time on a heated column.
- the BTU or energy content is calculated by summing up the concentration of the different hydrocarbon species and applying published mathematical equations.
- NIR based analysis operates on a different principle.
- a spectrum of the sample is collected. Light at different wavelengths is absorbed based on the concentration of functional groups, such as C—H, C ⁇ C—H, C ⁇ C—H, N—H, and O—H, present in the molecules of the gas.
- the spectrum of the natural gas is a sum of the different species present such as methane, ethane, isobutene, n-butane, propane, etc.
- Mathematical models based on chemometrics derive a relationship between the spectra and the concentration of the property of interest, such as BTU or energy content.
- the resulting calibration model is applied to each spectrum from the gas, and the BTU content can be reported to a local control or data logging system.
- the invention features a system of gas property monitoring. It comprises a gas cell for containing a gas of interest and a semiconductor tunable laser spectroscopy system for generating a tunable signal that is transmitted through the gas of interest in the gas cell and detecting the tunable signal after transmission through the gas of interest.
- An analyzer is provided for relating a spectral response of the gas of interest to a property of interest, such as an energy content of the gas of interest.
- a pressure sensor for determining a pressure of the gas of interest and a temperature sensor for determining a temperature of the gas of interest are further provided.
- the analyzer may use the pressure and the temperature to normalize the spectra before chemometric analysis is used to determine the property of interest.
- a hydrogen concentration sensor is provided. This sensor is used to detect the presence and amount of hydrogen in the gas of interest to address the situation where the narrow spectral signatures of the hydrogen are not able to be accurately detected by the broader spectral linewidth of the tunable laser.
- FIG. 1 is a schematic diagram showing a BTU or energy-content monitoring system according to an embodiment of the invention
- FIG. 2 is block diagram of the spectroscopy system of the monitoring system according to an embodiment of the invention.
- FIG. 3 illustrates an external cavity laser used in the spectroscopy system of one embodiment
- FIG. 4 is a plot showing the spectral response of exemplary natural gas components.
- FIG. 1 shows a system configuration for a BTU or energy-content monitoring system 10 , which has been constructed according to the principles of the present.
- the system 10 comprises a spectroscopy system 100 , enclosed in an explosion proof enclosure 12 .
- the spectroscopy system 100 further comprises a wireless data interface 11 , supporting an 802.11b communications interface for control of the spectroscopy system and for uploading of spectroscopic data from the system 100 to an analyzer computer 101 .
- the spectroscopy measurements are taken in a gas cell 14 .
- the cell 14 is designed to operate in the wavelength range from 1550-1800 nanometers (nm) at ambient temperatures (0 to +50° C.) and pressures up to 600 pounds per square inch (psi). Under normal operating conditions, the cell 14 will be at ambient ( ⁇ 60° C.) temperature and 100 psi.
- Two stainless steel-clad fiber optic cables 16 , 18 connect the spectroscopy system 100 to the gas cell 14 .
- the configuration is suitable for monitoring of natural gas.
- a tunable laser signal from the spectroscopy system 100 is transmitted to the gas cell 14 in output cable 16 .
- the tunable laser signal then propagates through the gas atmosphere in the gas cell 14 .
- the laser signal is then collected into the input cable 18 for transmission to the spectroscopic system detector 100 .
- the light output from the spectroscopy system 100 on the output fiber 16 which is single mode optical fiber with polarization control such as polarization maintaining or other polarization controlling fiber.
- a sample probe/tap 20 is installed into the gas line 22 . This extracts a representative sample of gas and transports it to a sample conditioning system 24 .
- the sample conditioning system 24 removes water and any condensate present, using a filter 26 . It also controls the pressure and flow to/through the gas cell using a first flow/pressure control valve 28 and a second flow/pressure control valve 36 .
- a pressure sensor 30 and a temperature sensor 32 are also installed in-line with the sample cell 14 .
- the pressure and temperature sensors 30 , 32 are read by the analyzer 101 and logged to enable compensation of the spectroscopy data based on a pressure and temperature.
- a hydrogen concentration sensor 33 is provided in line with the pressure and temperature sensors 30 , 32 .
- This hydrogen sensor is used to detect the presence and amount of hydrogen gas, diatomic hydrogen, in the gas of interest to address the situation where the narrow spectral signatures of the hydrogen are not able to be accurately detected by the broader spectral linewidth of the tunable laser of the spectroscopy system 100 .
- the gas of interest continuously flows through the flow cell 14 and is scanned and analyzed. After exiting the gas cell, the gas can be returned to a low pressure point 42 .
- a valve or restrictor 40 is used to create a pressure gradient between a high pressure region 38 , where the gas sample is drawn from, and the low pressure region 42 where the gas is returned to the pipe 22 .
- the sampled gas is flared.
- the analyzer 101 contains mathematical models based on chemometrics that relate the spectral data from the spectroscopy system 100 , the temperature data from temperature sensor 32 , hydrogen concentration from the hydrogen detector 33 , and pressure data from pressure 30 to the concentration of the property of interest, such as BTU or energy content.
- the resulting calibration model is applied to each spectrum generated by the spectroscopy system 100 from the gas in the gas cell 14 , and the BTU concentration is reported to a local control or data logging system.
- FIG. 2 shows the spectroscopy system 100 according to one embodiment. This system is discussed in more detail in U.S. patent application Ser. No. 11/419,993, filed May 23, 2006, by Flanders, et al., which is incorporated herein by this reference in its entirety.
- two tunable semiconductor sources 50 - 1 and 50 - 2 are provided to generate tunable signals in different, adjacent spectral bands to increase spectral range. In a current embodiment, only a single source is used that emits in the range from 1550 to 1800 nm.
- the tunable sources 50 - 1 , 50 - 2 have corresponding semiconductor chips 230 that are paired with microelectromechanical (MEMS) Fabry Perot tunable filters 200 to create external cavity tunable lasers (ECL).
- MEMS microelectromechanical
- Each of semiconductor sources 230 and tunable filters 200 of the tunable sources 50 - 1 , 50 - 2 are controlled by a system controller 60 .
- a digital signal processor core 61 drives the sources and tunable filters via separate digital to analog converters D/A 140 , 142 .
- Respective single mode optical fibers 52 - 1 and 52 - 2 carry the tunable signals from each of the sources 50 - 1 , 50 - 2 .
- a wavelength amplitude referencing system 102 combines the tunable signals from each of the sources 50 - 1 , 50 - 2 onto the output fiber 16 while also performing amplitude and wavelength detection.
- a polarizing beam combiner 110 is used to combine the tunable signals for each of the sources.
- a wavelength reference tap 105 directs a portion of the combined beam to a quartz reference etalon 111 and a wavelength reference detector 112 .
- An amplitude reference tap 116 directs a portion of the combined beam to an amplitude reference detector 114 .
- Each of these detectors 112 , 114 is monitored by the system controller 60 via separate analog to digital converters 62 , 64 .
- the tunable filters 200 are continuously scanned over the spectral scan band.
- the tunable signal is transmitted to the gas sample of interest in gas cell 14 via the output optical fiber 16 .
- the tunable signal from the sample is then collected on the input fiber and transmitted to a signal detector 70 , connected to the input fiber 18 , is then digitized by the detector's analog to digital converter 66 .
- the typical measurement time is less than 2 seconds (with signal averaging).
- the digital to analog converter 66 samples the detector 70 to provide a resolution of greater than 3.5 cm ⁇ 1 .
- every point of every scan is referenced.
- the signal from the wavelength reference detector 112 is a fringe pattern, analogous to the He-Ne reference signal in an FT-IR. This provides real-time wavelength referencing.
- An optical bench 104 on which the reference system 102 is implemented is thermostat-controlled, ensuring both short- and long-term dimensional stability for the etalon 110 , and thus both short- and long-term wavelength reproducibility.
- FIG. 3 illustrates an embodiment of the tunable ECL's in the tunable sources 50 - 1 , 50 - 2 .
- This ECL system is discussed in more detail in U.S. patent application Ser. No. 11/158,617, filed Jun. 22, 2005, by Flanders, et al., which is incorporated herein by this reference in its entirety.
- a reflective SOA 230 is used.
- a first mirror of the laser cavity 236 is a facet 234 of the SOA gain chip 230 that has a highly reflecting (HR) coating 232 .
- the other mirror of the laser cavity 236 is provided by an angled MEMS Fabry-Perot tunable filter 200 comprising an opposed curved mirror 212 and a flat mirror 210 .
- An intracavity lens 238 is used to collimate or collect the light from an AR coated facet 240 of the SOA 230 and generally form a beam waist 242 to launch the light into the resonant filter 200 and then couple light from the filter 200 back into the chip 230 .
- the light output from the laser cavity 236 is provided to the output fiber 16 , which is single mode fiber with polarization control such as polarization maintaining or other polarization controlling fiber.
- FIG. 4 shows the spectral responses of some representative components of natural gas and other hydrocarbons. As illustrated, the CH range, from 1550 to 1800 nm provides unique signatures for the components, while having relatively low water absorption.
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- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
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Abstract
Description
Claims (17)
Priority Applications (1)
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US11/613,291 US7764379B1 (en) | 2005-12-20 | 2006-12-20 | Semiconductor laser natural gas analysis system and method |
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US75230305P | 2005-12-20 | 2005-12-20 | |
US77546506P | 2006-02-21 | 2006-02-21 | |
US11/613,291 US7764379B1 (en) | 2005-12-20 | 2006-12-20 | Semiconductor laser natural gas analysis system and method |
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US7764379B1 true US7764379B1 (en) | 2010-07-27 |
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Cited By (7)
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WO2013023426A1 (en) * | 2011-08-18 | 2013-02-21 | 天津大学 | Multiband aliased inner cavity gas sensing system and sensing method |
US20130230271A1 (en) * | 2012-03-05 | 2013-09-05 | Pukyong National University Industry-University Cooperation Foundation | Optical Fiber Hydrogen Sensor and Method of Measuring Hydrogen Concentration Using the Same |
US20140326049A1 (en) * | 2013-05-06 | 2014-11-06 | Serguei Zelepouga | Method and apparatus for real-time measurement of fuel gas compositions and heating values |
US9869634B2 (en) | 2014-08-27 | 2018-01-16 | General Electric Company | System and method for dissolved gas analysis |
US10024768B1 (en) * | 2016-06-17 | 2018-07-17 | Markwest Energy Partners, L.P. | System, method, and apparatus for determining air emissions during pig receiver depressurization |
US10094781B2 (en) | 2014-04-14 | 2018-10-09 | General Electric Company | Methods and systems to analyze a gas-mixture |
US20220074850A1 (en) * | 2020-09-04 | 2022-03-10 | Carrier Corporation | Gas detection system |
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